CN111933932A - Ion liquid-assisted in-situ composite ZnV (zinc oxide) with specific crystal face growth in zinc ion battery2O6Method for preparing/GN-SWCNTS material - Google Patents

Ion liquid-assisted in-situ composite ZnV (zinc oxide) with specific crystal face growth in zinc ion battery2O6Method for preparing/GN-SWCNTS material Download PDF

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CN111933932A
CN111933932A CN202010793424.3A CN202010793424A CN111933932A CN 111933932 A CN111933932 A CN 111933932A CN 202010793424 A CN202010793424 A CN 202010793424A CN 111933932 A CN111933932 A CN 111933932A
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CN111933932B (en
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孙嬿
李春生
金奕
付俊龙
吴海涛
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Suzhou University of Science and Technology
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    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/16—Oxides
    • C30B29/22—Complex oxides
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
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    • C30B28/04—Production of homogeneous polycrystalline material with defined structure from liquids
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
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    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to an ionic liquid auxiliary source in a zinc ion batteryZnV growing on the site-recombination specific crystal face2O6GN-SWCNTS material. The method adopts a high specific surface area graphene/single-wall carbon nanotube material and trihexyltetradecylphosphonium chloride ([ P6, 6, 6, 14)][Cl]) The ionic liquid, zinc nitrate and ammonium metavanadate are used as raw materials, and the ionic liquid assisted microwave radiation method is adopted to grow ZnV on the surface of the graphene by compounding specific crystal faces in situ2O6The nanorod is 40-80 nm in diameter and 20-30 um in length. The ionic liquid-assisted microwave radiation method has the advantages of uniform surface adhesion of the composite material, simple operation, short reaction time, high efficiency, energy conservation and easy regulation and control of experimental parameters, and the ZnV prepared by the method2O6The nano composite electrode material has high specific area and good conductivity, shows good zinc storage performance when being used as a positive electrode material in a zinc ion battery, and provides good technical basis and practical experience for improving the comprehensive electrochemical performance of the zinc ion battery.

Description

Ion liquid-assisted in-situ composite ZnV (zinc oxide) with specific crystal face growth in zinc ion battery2O6Method for preparing/GN-SWCNTS material
Technical Field
The invention relates to the field of preparation and application of nano materials, in particular to ZnV (zinc oxide) grown by ionic liquid assisted in-situ compounding of specific crystal faces in a zinc ion battery2O6Method for preparing/GN-SWCNTS material
Background
In recent years, with the rapid development of smart grids and electric vehicles and the increasing preference of human beings for intermittent renewable energy sources such as solar energy, wind energy, tidal energy, geothermal energy and the like, the development of large-scale energy storage power stations is imperative. The zinc ion battery as a novel secondary battery not only has excellent electrochemical performance potential, but also gives consideration to social and economic evaluation indexes such as low price, environmental protection, friendliness and abundant resources, and is one of ideal choices of the next generation of large-scale energy storage technology. High-purity metal zinc is used as a negative electrode in the zinc ion battery, and the electrolyte contains Zn2+The positive electrode material of the aqueous solution can be a zinc-containing compound such as a vanadium-based compound, a manganese-based compound, a prussian blue analogue and the like. Inside the zinc ion battery, Zn2+Can be reversibly and rapidly inserted and removed in the anode material and realize Zn2+The electrolyte is efficiently deposited and dissolved in the electrolyte containing Zn2+ to complete the charging and discharging procedures, and finally the application requirements of energy storage and conversion are met. Of interest are ZnV2O6The positive electrode material used in the zinc ion battery has good structural stability and excellent electrochemical energy storage capacity and ion reversible de-intercalation capacity; but the characteristics of low specific surface area of the body material, poor conductivity and the like of the body material lead to the actual specific capacity of the zinc ion batteryLow and poor cycle stability. Thus, the positive electrode material ZnV2O6Conductivity optimization and small-size are important ways to enhance the zinc storage capacity of materials and improve the comprehensive electrochemical performance of zinc ion batteries (Y.Sun, C.S.Li, Q.R.Yang, S.L. Chou, H.K.Liu, electrochim.acta, 2016, 205, 62-69).
ZnV for zinc ion battery2O6As the cathode material, a hydrothermal (solvent) method, a high-temperature solid phase method, etc., a photocatalytic method, a deposition method, etc. (A.Bafaqeer, M.Tahir, N.A.S.Amin, J.appl.Catal.B-Enviro., 2019, 242, 312-. However, the traditional process can quickly synthesize ZnV with uniform size and regular appearance2O6There are also certain scientific and technical difficulties in the aspect of nano materials. It is worth to be researched that the ionic liquid assisted microwave radiation method has obvious advantages in the aspect of efficiently and controllably preparing the nano material, and the microwave radiation can rapidly transfer heat, so that ZnV can be caused2O6Dielectric heat effect is generated due to dielectric loss in an electromagnetic field, so that the nucleation reaction is accelerated, the reaction aging time is shortened, and the in-situ synthesis efficiency of the composite material is improved; through continuous adjustment of the ionic liquid and the parameters of the reaction system, the dimension, the loading capacity, the size and the surface property of the nanocrystalline can be effectively regulated and controlled, and a new research idea is provided for synthesis and application performance optimization of the nano material.
Based on the consideration, the invention provides an ionic liquid assisted microwave radiation method for synthesizing in-situ composite specific crystal face ZnV2O6GN-SWCNTS; it uses trihexyltetradecylphosphine chloride ([ P6, 6, 6, 14)][Cl]) Ionic liquids
Figure BSA0000216213380000021
Superfine ZnV grown by compounding specific crystal face on graphene surface in situ by auxiliary microwave radiation method2O6And (4) nanorods. Trihexyltetradecylphosphonium chloride ([ P6, 6, 6, 14)][Cl]) The ionic liquid is a structure directing agent of microwave radiation, has important effects on phase control and growth of the nano material, can realize optimization of the composition of a target product, and the obtained product has small size, uniform shape and excellent structure; the microwave radiation synthesis process has the outstanding advantages of short reaction time, simple operation, energy conservation, high efficiency, easy regulation and control of experimental parameters and the like. ZnV synthesized by ionic liquid assisted microwave radiation method2O6The nanorod material is high in specific area and good in conductivity, shows excellent zinc storage performance, effectively increases the specific capacity of the zinc ion battery, improves the cycling stability, and provides good technical basis and practical experience for improving the comprehensive electrochemical performance of the zinc ion battery.
Disclosure of Invention
Aiming at ZnV in zinc ion battery2O6The invention provides a zinc ion battery in which ionic liquid is used for assisting in-situ compounding of a specific crystal face to grow ZnV, and solves the problems of low specific surface area and poor conductivity of a positive electrode material2O6GN-SWCNTS material. The process has the advantages of short reaction time, simple operation, energy conservation, high efficiency, easily regulated experimental parameters and the prepared ZnV2O6ZnV in/GN-SWCNTS material2O6The nano-rod has uniform size, regular appearance, excellent structure, high specific area of the composite material and excellent conductivity, and optimizes the comprehensive electrochemical performance of the zinc ion battery.
The technical scheme of the invention is as follows: the invention provides a ZnV (zinc-ion battery) grown by ionic liquid assisted in-situ compounding of specific crystal face2O6Method for preparing/GN-SWCNTS material with high specific surface area graphene/single-walled carbon nanotube material, trihexyltetradecylphosphonium chloride ([ P6, 6, 6, 14)][Cl]) The ionic liquid, the zinc nitrate and the ammonium metavanadate are used as raw materials, and the microwave radiation method is adopted to compound ZnV with a specific crystal face on the surface of the graphene in situ to grow2O6The nanorod is used as a zinc ion battery anode material and shows good zinc storage performance, and a good technical effect is obtained; the method comprises the following steps:
firstly, in order to improve the conductivity of the material, a conductive carbon material is added in the experimental process; carbon atomThe material is a graphene/multi-wall carbon nanotube material with high specific surface area, and the specific surface area of the material is 1200-1800 m2The graphene ultrathin nanosheets are assembled by crosslinked graphene nanosheets with the interlayer spacing of 0.37nm, and single-walled carbon nanotubes with the diameter of 3-5 nm are inlaid on the surfaces of the graphene ultrathin nanosheets;
secondly, weighing 0.1000-1.0000 g of graphene powder material at room temperature, and adding the graphene powder material into 50ml of distilled water; then adding 0.2000g of trihexyltetradecylphosphine chloride ([ P6, 6, 6, 14] [ Cl ]) ionic liquid analytically pure raw material, and fully stirring for 1 hour to form uniform suspension a;
thirdly, transferring the suspension a obtained in the second step into a 200ml quartz round-bottom flask, assembling the flask into a normal-pressure microwave reactor with a reflux device, controlling the reaction temperature to be 80-100 ℃, adjusting the power of the device to be 500-1200 watts, and heating for 1 hour to obtain an adsorbed suspension b; in the step, the core innovation point is that under the action of a microwave field, the surface of the graphene/multi-walled carbon nanotube is effectively adsorbed with ionic liquid, so that experimental conditions are provided for the subsequent in-situ one-dimensional nano material oriented growth;
fourthly, 0.5850g of NH was added to the post-adsorption suspension b4VO3Stirring ammonium metavanadate solid for 1 hour until the ammonium metavanadate solid is completely dissolved to form a suspension c; transferring the suspension c obtained in the fourth step into a normal-pressure microwave reactor with a reflux device again, controlling the reaction temperature to be 80-100 ℃, adjusting the power of the equipment to be 500-1200 watts, and heating for 10min to obtain a suspension d subjected to secondary adsorption; in the secondary microwave reaction step, the core innovation point is that the vanadate is arranged at [ P6, 6, 6, 14]][Cl]The ionic liquid containing phosphine functional groups is further adsorbed on the surface of the graphene/multi-walled carbon nanotube under the action of microwave radiation, so that the ordered crystal growth along a specific crystal face is facilitated in the next reaction process;
fifthly, adding a zinc nitrate solution with the solution volume of 50ml and the molar concentration of 0.20mol/L into the suspension d after adsorption, fully stirring for 20 minutes, continuously transferring the suspension into a normal-pressure microwave reactor with a reflux device, controlling the reaction temperature to be 80-100 ℃, adjusting the heating power of equipment to be 500-1200 watts, and heatingThe time is 8 hours, the black agglomerated suspension e is obtained, after the obtained suspension e is slowly cooled to the room temperature, the suspension e is washed by distilled water for 4 times, rinsed by ethanol for 1 time, and placed in a vacuum drying oven at the temperature of 80 ℃ for drying for 24 hours; dried black solid sample: zinc vanadate nanorods/graphene/multiwalled carbon nanotubes; x-ray diffraction tests show that: the phase of the material is monoclinic phase m-ZnV2O6Corresponding to cell parameters of
Figure BSA0000216213380000031
And β 111.55 °, space point group: c2(No.5), the number of the ICDD-JCPDS card is No. 74-1262; SEM test shows that: m-ZnV2O6The nanorod is 40-80 nm in diameter and 20-30 microns in length, and is embedded on the surface of the graphene/multi-walled carbon nanotube in situ; HRTEM analysis and test show that m-ZnV2O6The growth direction of the nanorods is along [010 ]]Directionally preferential growth.
Sixthly, in order to test the energy storage performance of the zinc vanadate nanorod/graphene/multi-walled carbon nanotube in the zinc ion battery, assembling the electrode material into a CR2032 button cell; the working electrode is prepared by uniformly stirring a zinc vanadate nanorod/graphene/multi-walled carbon nanotube battery material, SP conductive carbon black and polyvinylidene fluoride powder according to a formula with the weight ratio of 8: 1, and the dispersing solvent is N-methyl pyrrolidone, and stirring for 2 hours to form a uniform paste; uniformly coating the aluminum foil on a high-purity aluminum foil, and drying the aluminum foil in a vacuum drying oven at 120 ℃ for 12 hours to obtain an electrode slice; the water electrolyte is preferably 0.2-0.5 mol/L ZnSO4A solution; the counter electrode is a metal zinc sheet with the purity of 99.99 percent; the test of 0.1C constant current charging and discharging performance and the test of cycling stability show that: the material has good zinc storage capacity and capacity retention rate, and the comprehensive performance obtains good and excellent effects.
The invention has the advantages and effects that: the invention relates to an ionic liquid assisted in-situ composite ZnV with specific crystal face growth in a zinc ion battery2O6The method for preparing the/GN-SWCNTS material has the following beneficial advantages and effects: 1. the invention adopts an ionic liquid assisted microwave radiation method to synthesize and prepare in-situ composite ZnV with a specific crystal face2O6The method for preparing the/GN-SWCNTS material has the advantages of short reaction time, simple operation, energy conservation, high efficiency, easy regulation and control of experimental parameters, uniform dispersion degree of the composite material and high product purity. 2. m-ZnV in the prepared anode composite material2O6The nanorod is 40-80 nm in diameter and 20-30 microns in length, is embedded on the surface of the graphene/multi-walled carbon nanotube in situ, and effectively improves the electron conduction performance of the material; 3. in-situ compounding of specific crystal face ZnV2O6The GN-SWCNTS material has the characteristics of showing good cycle stability and discharge performance in the zinc ion battery, and providing valuable basis for improving the comprehensive electrochemical performance of the zinc ion battery.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image at 10K magnification of GN-SWCTs starting material
FIG. 2 is a high-magnification SEM image at 100K magnification of GN-SWCTs starting material
FIG. 3 is a super-high SEM image of GN-SWCTs feedstock at 300K magnification
FIG. 4 is a partial high-magnification SEM image at 500K magnification of GN-SWCTs raw material
Firstly, in order to improve the conductivity of the material, a conductive carbon material is added in the experimental process; the carbon raw material is a graphene/multi-wall carbon nanotube material with high specific surface area, and the specific surface area of the material is 1200-1800 m2The graphene ultrathin nanosheets are assembled by crosslinked graphene nanosheets with the interlayer spacing of 0.37nm, and single-walled carbon nanotubes with the diameter of 3-5 nm are inlaid on the surfaces of the graphene ultrathin nanosheets; secondly, weighing 0.1000-1.0000 g of graphene powder material at room temperature, and adding the graphene powder material into 50ml of distilled water; 0.2000g of trihexyltetradecylphosphine chloride ([ P6, 6, 6, 14) was additionally added][Cl]) Analyzing pure raw materials by using ionic liquid, and fully stirring for 1 hour to form uniform suspension a; thirdly, transferring the suspension a obtained in the second step into a 200ml quartz round-bottom flask, assembling the flask into a normal-pressure microwave reactor with a reflux device, controlling the reaction temperature to be 80-100 ℃, adjusting the power of the device to be 500-1200 watts, and heating for 1 hour to obtain an adsorbed suspension b; in the step, the core innovation point is that the graphene/poly-graphene is subjected to the action of a microwave fieldThe surface of the wall carbon nanotube effectively adsorbs ionic liquid, and experimental conditions are provided for the subsequent in-situ one-dimensional nano material oriented growth; fourthly, 0.5850gNH was added to the post-adsorption suspension b4VO3Stirring ammonium metavanadate solid for 1 hour until the ammonium metavanadate solid is completely dissolved to form a suspension c; transferring the suspension c obtained in the fourth step into a normal-pressure microwave reactor with a reflux device again, controlling the reaction temperature to be 80-100 ℃, adjusting the power of the equipment to be 500-1200 watts, and heating for 10min to obtain a suspension d subjected to secondary adsorption; in the secondary microwave reaction step, the core innovation point is that the vanadate is arranged at [ P6, 6, 6, 14]][Cl]The ionic liquid containing phosphine functional groups is further adsorbed on the surface of the graphene/multi-walled carbon nanotube under the action of microwave radiation, so that the ordered crystal growth along a specific crystal face is facilitated in the next reaction process; fifthly, adding a zinc nitrate solution with the volume of 50ml and the molar concentration of 0.20mol/L into the adsorbed suspension d, fully stirring for 20 minutes, continuously transferring the suspension into a normal-pressure microwave reactor with a reflux device, controlling the reaction temperature to be 80-100 ℃, adjusting the heating power of equipment to be 500-1200 watts, heating for 8 hours, obtaining a black agglomerated suspension e, slowly cooling the obtained suspension e to room temperature, washing the black agglomerated suspension e with distilled water for 4 times, rinsing the black agglomerated suspension e with ethanol for 1 time, and drying the black agglomerated suspension e in a vacuum drying oven at 80 ℃ for 24 hours; dried black solid sample: zinc vanadate nanorods/graphene/multiwalled carbon nanotubes; x-ray diffraction tests show that: the phase of the material is monoclinic phase m-ZnV2O6Corresponding to cell parameters of
Figure BSA0000216213380000051
And β 111.55 °, space point group: c2(No.5), the number of the ICDD-JCPDS card is No. 74-1262; SEM test shows that: m-ZnV2O6The nanorod is 40-80 nm in diameter and 20-30 microns in length, and is embedded on the surface of the graphene/multi-walled carbon nanotube in situ; HRTEM analysis and test show that m-ZnV2O6The growth direction of the nanorods is along [010 ]]Directionally dominant growth; sixthly, testing the energy storage performance of the zinc vanadate nanorod/graphene/multi-walled carbon nanotube in the zinc ion batteryThe electrode material is assembled into a CR2032 button cell; the working electrode is prepared by uniformly stirring a zinc vanadate nanorod/graphene/multi-walled carbon nanotube battery material, SP conductive carbon black and polyvinylidene fluoride powder according to a formula with the weight ratio of 8: 1, and the dispersing solvent is N-methyl pyrrolidone, and stirring for 2 hours to form a uniform paste; uniformly coating the aluminum foil on a high-purity aluminum foil, and drying the aluminum foil in a vacuum drying oven at 120 ℃ for 12 hours to obtain an electrode slice; the aqueous electrolyte is preferably 0.5mol/L ZnSO4A solution; the counter electrode is a metal zinc sheet with the purity of 99.99 percent; the test of 0.1C constant current charging and discharging performance and the test of cycling stability show that: the material has good zinc storage capacity and capacity retention rate, and the comprehensive performance obtains good and excellent effects.
Detailed Description
Example 1: 0.1000g of graphene powder material, the reflux reaction temperature is 100 ℃, the microwave power is 800W, and in order to improve the conductivity of the material, a conductive carbon material is added in the experimental process; the carbon raw material is a high specific surface area graphene/multi-wall carbon nanotube material, and the specific surface area of the material is 1600m2The graphene ultrathin nanosheets are assembled by crosslinked graphene nanosheets with the interlayer spacing of 0.37nm, and single-walled carbon nanotubes with the diameter of 3-5 nm are inlaid on the surfaces of the graphene ultrathin nanosheets; secondly, weighing 0.1000g of graphene powder material at room temperature, and adding the graphene powder material into 50ml of distilled water; 0.2000g of trihexyltetradecylphosphine chloride ([ P6, 6, 6, 14) was additionally added][Cl]) Analyzing pure raw materials by using ionic liquid, and fully stirring for 1 hour to form uniform suspension a; thirdly, transferring the suspension a obtained in the second step into a 200ml quartz round-bottom flask, assembling the flask into a normal-pressure microwave reactor with a reflux device, controlling the reaction temperature at 100 ℃, adjusting the power of the device at 800 watts, and heating for 1 hour to obtain an adsorbed suspension b; in the step, the core innovation point is that under the action of a microwave field, the surface of the graphene/multi-walled carbon nanotube is effectively adsorbed with ionic liquid, so that experimental conditions are provided for the subsequent in-situ one-dimensional nano material oriented growth; fourthly, 0.5850g of NH was added to the post-adsorption suspension b4VO3Stirring ammonium metavanadate solid for 1 hour until the ammonium metavanadate solid is completely dissolved to form a suspension c; the suspension c obtained in the fourth step is again subjected toTransferring to a normal pressure microwave reactor with a reflux device, controlling the reaction temperature at 100 ℃, adjusting the power of the equipment at 800 watts, and heating for 10min to obtain a suspension d subjected to secondary adsorption; in the secondary microwave reaction step, the core innovation point is that the vanadate is arranged at [ P6, 6, 6, 14]][Cl]The ionic liquid containing phosphine functional groups is further adsorbed on the surface of the graphene/multi-walled carbon nanotube under the action of microwave radiation, so that the ordered crystal growth along a specific crystal face is facilitated in the next reaction process; fifthly, adding a zinc nitrate solution with the volume of 50ml and the molar concentration of 0.20mol/L into the adsorbed suspension d, fully stirring for 20 minutes, continuously transferring the suspension into a normal-pressure microwave reactor with a reflux device, controlling the reaction temperature at 100 ℃, adjusting the heating power of equipment at 800 watts, heating for 8 hours, obtaining a black agglomerated suspension e, slowly cooling the obtained suspension e to the room temperature, washing the suspension e with distilled water for 4 times, rinsing the suspension e with ethanol for 1 time, and drying the suspension e in a vacuum drying oven at 80 ℃ for 24 hours; dried black solid sample: zinc vanadate nanorods/graphene/multiwalled carbon nanotubes; x-ray diffraction tests show that: the phase of the material is monoclinic phase m-ZnV2O6Corresponding to cell parameters of
Figure BSA0000216213380000061
Figure BSA0000216213380000062
And β 111.55 °, space point group: c2(No.5), the number of the ICDD-JCPDS card is No. 74-1262; SEM test shows that: m-ZnV2O6The nanorod is 40-80 nm in diameter and 20-30 microns in length, and is embedded on the surface of the graphene/multi-walled carbon nanotube in situ; HRTEM analysis and test show that m-ZnV2O6The growth direction of the nanorods is along [010 ]]Directionally dominant growth; sixthly, in order to test the energy storage performance of the zinc vanadate nanorod/graphene/multi-walled carbon nanotube in the zinc ion battery, assembling the electrode material into a CR2032 button cell; the working electrode is prepared by uniformly stirring a zinc vanadate nanorod/graphene/multi-walled carbon nanotube battery material, SP conductive carbon black and polyvinylidene fluoride powder according to a formula with the weight ratio of 8: 1The dispersing solvent is N-methyl pyrrolidone, and the uniform paste is formed after 2 hours of stirring; uniformly coating the aluminum foil on a high-purity aluminum foil, and drying the aluminum foil in a vacuum drying oven at 120 ℃ for 12 hours to obtain an electrode slice; the aqueous electrolyte is preferably 0.5mol/L ZnSO4A solution; the counter electrode is a metal zinc sheet with the purity of 99.99 percent; the test of 0.1C constant current charging and discharging performance and the test of cycling stability show that: the material has good zinc storage capacity and capacity retention rate, and the comprehensive performance obtains good and excellent effects.
Example 2: 0.5500g of graphene powder material, the reflux reaction temperature is 100 ℃, and the microwave power is 1000 watts
Firstly, in order to improve the conductivity of the material, a conductive carbon material is added in the experimental process; the carbon raw material is a high specific surface area graphene/multi-wall carbon nanotube material, and the specific surface area of the material is 1600m2The graphene ultrathin nanosheets are assembled by crosslinked graphene nanosheets with the interlayer spacing of 0.37nm, and single-walled carbon nanotubes with the diameter of 3-5 nm are inlaid on the surfaces of the graphene ultrathin nanosheets; secondly, weighing 0.5500g of graphene powder material at room temperature, and adding the graphene powder material into 50ml of distilled water; 0.2000g of trihexyltetradecylphosphine chloride ([ P6, 6, 6, 14) was additionally added][Cl]) Analyzing pure raw materials by using ionic liquid, and fully stirring for 1 hour to form uniform suspension a; thirdly, transferring the suspension a obtained in the second step into a 200ml quartz round-bottom flask, assembling the flask into a normal-pressure microwave reactor with a reflux device, controlling the reaction temperature at 100 ℃, adjusting the power of the device at 800 watts, and heating for 1 hour to obtain an adsorbed suspension b; in the step, the core innovation point is that under the action of a microwave field, the surface of the graphene/multi-walled carbon nanotube is effectively adsorbed with ionic liquid, so that experimental conditions are provided for the subsequent in-situ one-dimensional nano material oriented growth; fourthly, 0.5850g of NH was added to the post-adsorption suspension b4VO3Stirring ammonium metavanadate solid for 1 hour until the ammonium metavanadate solid is completely dissolved to form a suspension c; transferring the suspension c obtained in the fourth step to a normal-pressure microwave reactor with a reflux device again, controlling the reaction temperature at 100 ℃, adjusting the power of the equipment at 1000 watts, and heating for 10min to obtain a suspension d subjected to secondary adsorption; in the secondary microwave reaction step, the core is createdThe new point is that the vanadate is arranged at [ P6, 6, 6, 14]][Cl]The ionic liquid containing phosphine functional groups is further adsorbed on the surface of the graphene/multi-walled carbon nanotube under the action of microwave radiation, so that the ordered crystal growth along a specific crystal face is facilitated in the next reaction process; fifthly, adding a zinc nitrate solution with the volume of 50ml and the molar concentration of 0.20mol/L into the adsorbed suspension d, fully stirring for 20 minutes, continuously transferring the suspension into a normal-pressure microwave reactor with a reflux device, controlling the reaction temperature at 100 ℃, adjusting the heating power of equipment at 1000 watts, heating for 8 hours, obtaining a black agglomerated suspension e, slowly cooling the obtained suspension e to the room temperature, washing the suspension e with distilled water for 4 times, rinsing the suspension e with ethanol for 1 time, and drying the suspension e in a vacuum drying oven at 80 ℃ for 24 hours; dried black solid sample: zinc vanadate nanorods/graphene/multiwalled carbon nanotubes; x-ray diffraction tests show that: the phase of the material is monoclinic phase m-ZnV2O6Corresponding to cell parameters of
Figure BSA0000216213380000081
Figure BSA0000216213380000082
And β 111.55 °, space point group: c2(No.5), the number of the ICDD-JCPDS card is No. 74-1262; SEM test shows that: m-ZnV2O6The nanorod is 40-80 nm in diameter and 20-30 microns in length, and is embedded on the surface of the graphene/multi-walled carbon nanotube in situ; HRTEM analysis and test show that m-ZnV2O6The growth direction of the nanorods is along [010 ]]Directionally dominant growth; sixthly, in order to test the energy storage performance of the zinc vanadate nanorod/graphene/multi-walled carbon nanotube in the zinc ion battery, assembling the electrode material into a CR2032 button cell; the working electrode is prepared by uniformly stirring a zinc vanadate nanorod/graphene/multi-walled carbon nanotube battery material, SP conductive carbon black and polyvinylidene fluoride powder according to a formula with the weight ratio of 8: 1, and the dispersing solvent is N-methyl pyrrolidone, and stirring for 2 hours to form a uniform paste; uniformly coating the aluminum foil on a high-purity aluminum foil, and drying the aluminum foil in a vacuum drying oven at 120 ℃ for 12 hours to obtain an electrode slice; the aqueous electrolyte is preferably 0.5mol/L ZnSO4A solution; the counter electrode is a metal zinc sheet with the purity of 99.99 percent; the test of 0.1C constant current charging and discharging performance and the test of cycling stability show that: the material has good zinc storage capacity and capacity retention rate, and the comprehensive performance obtains good and excellent effects.
Example 3: 1.0000g of graphene powder material, the reflux reaction temperature is 100 ℃, the microwave power is 1100 watts first, and in order to improve the conductivity of the material, a conductive carbon material is added in the experimental process; the carbon raw material is a high specific surface area graphene/multi-wall carbon nanotube material, and the specific surface area of the material is 1600m2The graphene ultrathin nanosheets are assembled by crosslinked graphene nanosheets with the interlayer spacing of 0.37nm, and single-walled carbon nanotubes with the diameter of 3-5 nm are inlaid on the surfaces of the graphene ultrathin nanosheets; secondly, weighing 1.0000g of graphene powder material at room temperature, and adding the graphene powder material into 50ml of distilled water; 0.2000g of trihexyltetradecylphosphine chloride ([ P6, 6, 6, 14) was additionally added][Cl]) Analyzing pure raw materials by using ionic liquid, and fully stirring for 1 hour to form uniform suspension a; thirdly, transferring the suspension a obtained in the second step into a 200ml quartz round-bottom flask, assembling the flask into a normal-pressure microwave reactor with a reflux device, controlling the reaction temperature at 100 ℃, adjusting the power of the device at 1100 watts, and heating for 1 hour to obtain an adsorbed suspension b; in the step, the core innovation point is that under the action of a microwave field, the surface of the graphene/multi-walled carbon nanotube is effectively adsorbed with ionic liquid, so that experimental conditions are provided for the subsequent in-situ one-dimensional nano material oriented growth; fourthly, 0.5850g of NH was added to the post-adsorption suspension b4VO3Stirring ammonium metavanadate solid for 1 hour until the ammonium metavanadate solid is completely dissolved to form a suspension c; transferring the suspension c obtained in the fourth step to a normal-pressure microwave reactor with a reflux device again, controlling the reaction temperature at 100 ℃, adjusting the power of the equipment at 1100 watts, and heating for 10min to obtain a suspension d subjected to secondary adsorption; in the secondary microwave reaction step, the core innovation point is that the vanadate is arranged at [ P6, 6, 6, 14]][Cl]The ionic liquid containing phosphine functional groups is further adsorbed on the surface of the graphene/multi-walled carbon nanotube under the action of microwave radiation, so that the ordered crystal growth along a specific crystal face is facilitated in the next reaction process; fifth, in the above-mentioned suctionAdding a zinc nitrate solution with the volume of 50ml and the molar concentration of 0.20mol/L into the attached suspension d, fully stirring for 20 minutes, continuously transferring into a normal-pressure microwave reactor with a reflux device, controlling the reaction temperature at 100 ℃, adjusting the heating power of the equipment at 1100 watts, heating for 8 hours to obtain a black agglomerated suspension e, slowly cooling the obtained suspension e to room temperature, washing the black agglomerated suspension e with distilled water for 4 times, rinsing the black agglomerated suspension e with ethanol for 1 time, and placing the black agglomerated suspension e in a vacuum drying oven at 80 ℃ for drying for 24 hours; dried black solid sample: zinc vanadate nanorods/graphene/multiwalled carbon nanotubes; x-ray diffraction tests show that: the phase of the material is monoclinic phase m-ZnV2O6Corresponding to cell parameters of
Figure BSA0000216213380000091
Figure BSA0000216213380000092
And β 111.55 °, space point group: c2(No.5), the number of the ICDD-JCPDS card is No. 74-1262; SEM test shows that: m-ZnV2O6The nanorod is 40-80 nm in diameter and 20-30 microns in length, and is embedded on the surface of the graphene/multi-walled carbon nanotube in situ; HRTEM analysis and test show that m-ZnV2O6The growth direction of the nanorods is along [010 ]]Directionally dominant growth; sixthly, in order to test the energy storage performance of the zinc vanadate nanorod/graphene/multi-walled carbon nanotube in the zinc ion battery, assembling the electrode material into a CR2032 button cell; the working electrode is prepared by uniformly stirring a zinc vanadate nanorod/graphene/multi-walled carbon nanotube battery material, SP conductive carbon black and polyvinylidene fluoride powder according to a formula with the weight ratio of 8: 1, and the dispersing solvent is N-methyl pyrrolidone, and stirring for 2 hours to form a uniform paste; uniformly coating the aluminum foil on a high-purity aluminum foil, and drying the aluminum foil in a vacuum drying oven at 120 ℃ for 12 hours to obtain an electrode slice; the aqueous electrolyte is preferably 0.5mol/L ZnSO4A solution; the counter electrode is a metal zinc sheet with the purity of 99.99 percent; the test of 0.1C constant current charging and discharging performance and the test of cycling stability show that: the material has good zinc storage capacity and capacity retention rate, and the comprehensive performance obtains good and excellent effects.
Example 4: 0.1000g of graphene powder material, the reflux reaction temperature is 100 DEG C
Firstly, in order to improve the conductivity of the material, a conductive carbon material is added in the experimental process; the carbon raw material is a high specific surface area graphene/multi-wall carbon nanotube material, and the specific surface area of the material is 1600m2The graphene ultrathin nanosheets are assembled by crosslinked graphene nanosheets with the interlayer spacing of 0.37nm, and single-walled carbon nanotubes with the diameter of 3-5 nm are inlaid on the surfaces of the graphene ultrathin nanosheets; secondly, weighing 0.1000g of graphene powder material at room temperature, and adding the graphene powder material into 50ml of distilled water; 0.2000g of trihexyltetradecylphosphine chloride ([ P6, 6, 6, 14) was additionally added][Cl]) Analyzing pure raw materials by using ionic liquid, and fully stirring for 1 hour to form uniform suspension a; thirdly, transferring the suspension a obtained in the second step into a 200ml quartz round-bottom flask, assembling the flask into a normal-pressure microwave reactor with a reflux device, controlling the reaction temperature at 100 ℃, adjusting the power of the device at 500 watts, and heating for 1 hour to obtain an adsorbed suspension b; in the step, the core innovation point is that under the action of a microwave field, the surface of the graphene/multi-walled carbon nanotube is effectively adsorbed with ionic liquid, so that experimental conditions are provided for the subsequent in-situ one-dimensional nano material oriented growth; fourthly, 0.5850gNH was added to the post-adsorption suspension b4VO3Stirring ammonium metavanadate solid for 1 hour until the ammonium metavanadate solid is completely dissolved to form a suspension c; transferring the suspension c obtained in the fourth step to a normal-pressure microwave reactor with a reflux device again, controlling the reaction temperature at 100 ℃, adjusting the power of the equipment at 500 watts, and heating for 10min to obtain a suspension d subjected to secondary adsorption; in the secondary microwave reaction step, the core innovation point is that the vanadate is arranged at [ P6, 6, 6, 14]][Cl]The ionic liquid containing phosphine functional groups is further adsorbed on the surface of the graphene/multi-walled carbon nanotube under the action of microwave radiation, so that the ordered crystal growth along a specific crystal face is facilitated in the next reaction process; fifthly, adding a zinc nitrate solution with the volume of 50ml and the molar concentration of 0.20mol/L into the suspension solution d after adsorption, fully stirring for 20 minutes, continuously transferring into a normal-pressure microwave reactor with a reflux device, controlling the reaction temperature at 100 ℃, adjusting the heating power of equipment at 500 watts,heating for 8 hours to obtain a black agglomerated suspension e, slowly cooling the suspension e to room temperature, washing the suspension e with distilled water for 4 times, rinsing the suspension e with ethanol for 1 time, and placing the suspension e in a vacuum drying oven at 80 ℃ to dry for 24 hours; dried black solid sample: zinc vanadate nanorods/graphene/multiwalled carbon nanotubes; x-ray diffraction tests show that: the phase of the material is monoclinic phase m-ZnV2O6Corresponding to cell parameters of
Figure BSA0000216213380000101
Figure BSA0000216213380000102
And β 111.55 °, space point group: c2(No.5), the number of the ICDD-JCPDS card is No. 74-1262; SEM test shows that: m-ZnV2O6The nanorod is 40-80 nm in diameter and 20-30 microns in length, and is embedded on the surface of the graphene/multi-walled carbon nanotube in situ; HRTEM analysis and test show that m-ZnV2O6The growth direction of the nanorods is along [010 ]]Directionally dominant growth; sixthly, in order to test the energy storage performance of the zinc vanadate nanorod/graphene/multi-walled carbon nanotube in the zinc ion battery, assembling the electrode material into a CR2032 button cell; the working electrode is prepared by uniformly stirring a zinc vanadate nanorod/graphene/multi-walled carbon nanotube battery material, SP conductive carbon black and polyvinylidene fluoride powder according to a formula with the weight ratio of 8: 1, and the dispersing solvent is N-methyl pyrrolidone, and stirring for 2 hours to form a uniform paste; uniformly coating the aluminum foil on a high-purity aluminum foil, and drying the aluminum foil in a vacuum drying oven at 120 ℃ for 12 hours to obtain an electrode slice; the aqueous electrolyte is preferably 0.5mol/L ZnSO4A solution; the counter electrode is a metal zinc sheet with the purity of 99.99 percent; the test of 0.1C constant current charging and discharging performance and the test of cycling stability show that: the material has good zinc storage capacity and capacity retention rate, and the comprehensive performance obtains good and excellent effects.
Example 5: 0.5500g of graphene powder material, and the reflux reaction temperature is 100 DEG C
Firstly, in order to improve the conductivity of the material, a conductive carbon material is added in the experimental process; the carbon raw material is high specific surface area graphene/multi-wallA carbon nanotube material having a specific surface area of 1800m2The graphene ultrathin nanosheets are assembled by crosslinked graphene nanosheets with the interlayer spacing of 0.37nm, and single-walled carbon nanotubes with the diameter of 3-5 nm are inlaid on the surfaces of the graphene ultrathin nanosheets; secondly, weighing 0.5500g of graphene powder material at room temperature, and adding the graphene powder material into 50ml of distilled water; 0.2000g of trihexyltetradecylphosphine chloride ([ P6, 6, 6, 14) was additionally added][Cl]) Analyzing pure raw materials by using ionic liquid, and fully stirring for 1 hour to form uniform suspension a; thirdly, transferring the suspension a obtained in the second step into a 200ml quartz round-bottom flask, assembling the flask into a normal-pressure microwave reactor with a reflux device, controlling the reaction temperature at 100 ℃, adjusting the power of the device at 800 watts, and heating for 1 hour to obtain an adsorbed suspension b; in the step, the core innovation point is that under the action of a microwave field, the surface of the graphene/multi-walled carbon nanotube is effectively adsorbed with ionic liquid, so that experimental conditions are provided for the subsequent in-situ one-dimensional nano material oriented growth; fourthly, 0.5850g of NH was added to the post-adsorption suspension b4VO3Stirring ammonium metavanadate solid for 1 hour until the ammonium metavanadate solid is completely dissolved to form a suspension c; transferring the suspension c obtained in the fourth step to a normal-pressure microwave reactor with a reflux device again, controlling the reaction temperature at 100 ℃, adjusting the power of the equipment at 800 watts, and heating for 10min to obtain a suspension d subjected to secondary adsorption; in the secondary microwave reaction step, the core innovation point is that the vanadate is arranged at [ P6, 6, 6, 14]][Cl]The ionic liquid containing phosphine functional groups is further adsorbed on the surface of the graphene/multi-walled carbon nanotube under the action of microwave radiation, so that the ordered crystal growth along a specific crystal face is facilitated in the next reaction process; fifthly, adding a zinc nitrate solution with the volume of 50ml and the molar concentration of 0.20mol/L into the adsorbed suspension d, fully stirring for 20 minutes, continuously transferring the suspension into a normal-pressure microwave reactor with a reflux device, controlling the reaction temperature at 100 ℃, adjusting the heating power of equipment at 800 watts, heating for 8 hours, obtaining a black agglomerated suspension e, slowly cooling the obtained suspension e to the room temperature, washing the suspension e with distilled water for 4 times, rinsing the suspension e with ethanol for 1 time, and drying the suspension e in a vacuum drying oven at 80 ℃ for 24 hours; dried black solid sample: zinc vanadate nanorodGraphene/multi-walled carbon nanotubes; x-ray diffraction tests show that: the phase of the material is monoclinic phase m-ZnV2O6Corresponding to cell parameters of
Figure BSA0000216213380000111
Figure BSA0000216213380000112
And β 111.55 °, space point group: c2(No.5), the number of the ICDD-JCPDS card is No. 74-1262; SEM test shows that: m-ZnV2O6The nanorod is 40-80 nm in diameter and 20-30 microns in length, and is embedded on the surface of the graphene/multi-walled carbon nanotube in situ; HRTEM analysis and test show that m-ZnV2O6The growth direction of the nanorods is along [010 ]]Directionally dominant growth; sixthly, in order to test the energy storage performance of the zinc vanadate nanorod/graphene/multi-walled carbon nanotube in the zinc ion battery, assembling the electrode material into a CR2032 button cell; the working electrode is prepared by uniformly stirring a zinc vanadate nanorod/graphene/multi-walled carbon nanotube battery material, SP conductive carbon black and polyvinylidene fluoride powder according to a formula with the weight ratio of 8: 1, and the dispersing solvent is N-methyl pyrrolidone, and stirring for 2 hours to form a uniform paste; uniformly coating the aluminum foil on a high-purity aluminum foil, and drying the aluminum foil in a vacuum drying oven at 120 ℃ for 12 hours to obtain an electrode slice; the aqueous electrolyte is preferably 0.5mol/L ZnSO4A solution; the counter electrode is a metal zinc sheet with the purity of 99.99 percent; the test of 0.1C constant current charging and discharging performance and the test of cycling stability show that: the material has good zinc storage capacity and capacity retention rate, and the comprehensive performance obtains good and excellent effects.
Comparative example 1 of example 1, university of Hebei Union, a method for synthesizing ZnV by high temperature solid phase method2O6And ZnV2O7The method and application of the micro-nano material are as follows: china, 201110287566.3[ P ]]2012-04-11 provides a method of preparing, comprising the steps of: in the method for synthesizing the zinc vanadate material by the high-temperature solid phase method, the ammonium metavanadate ultrafine powder is burnt in a muffle furnace for 4 hours at the temperature of 600 ℃ to obtain vanadium pentoxide ultrafine solid powder: weighing the prepared vanadium pentoxide powder and zinc oxide powder to obtain vanadium pentoxide powderThe mol ratio of the precursor to the zinc oxide is 1: 1, the two precursors are uniformly mixed, fully ground for 30 minutes, uniformly ground powder is molded on a tablet machine for 1 minute under the pressure of 10MPa, then the powder is placed in a muffle furnace for sintering for 6 hours at the temperature of 600 ℃, and the obtained product is ZnV shown by an X-ray diffraction spectrogram (figure 1)2O6And Zn2V2O7The corresponding card numbers are 23-757 and 24-1483, respectively, wherein the product ZnV2O6Is higher; the scanning electron microscope (figure 2) of the product shows that the appearance of the main body of the product is a micro-nano material with uniform size, and the diameter of the micro-nano material is distributed between 50 and 500 nanometers. The product prepared by the method has the problems of low purity, uneven size and high energy consumption, and the preparation of the composite material cannot be carried out.
While example 1 is combined with comparative example 1 without motivation, and example 1 has clear innovativeness and is represented by:
example 1: 0.1000g of graphene powder material, the reflux reaction temperature is 100 ℃, and the microwave power is 800 watts
Firstly, in order to improve the conductivity of the material, a conductive carbon material is added in the experimental process; the carbon raw material is a high specific surface area graphene/multi-wall carbon nanotube material, and the specific surface area of the material is 1600m2The graphene ultrathin nanosheets are assembled by crosslinked graphene nanosheets with the interlayer spacing of 0.37nm, and single-walled carbon nanotubes with the diameter of 3-5 nm are inlaid on the surfaces of the graphene ultrathin nanosheets; secondly, weighing 0.1000g of graphene powder material at room temperature, and adding the graphene powder material into 50ml of distilled water; 0.2000g of trihexyltetradecylphosphine chloride ([ P6, 6, 6, 14) was additionally added][Cl]) Analyzing pure raw materials by using ionic liquid, and fully stirring for 1 hour to form uniform suspension a; thirdly, transferring the suspension a obtained in the second step into a 200ml quartz round-bottom flask, assembling the flask into a normal-pressure microwave reactor with a reflux device, controlling the reaction temperature at 100 ℃, adjusting the power of the device at 800 watts, and heating for 1 hour to obtain an adsorbed suspension b; in the step, the core innovation point is that under the action of a microwave field, the surface of the graphene/multi-walled carbon nanotube is effectively adsorbed with ionic liquid, so that experimental conditions are provided for the subsequent in-situ one-dimensional nano material oriented growth; fourth, after the adsorption0.5850gNH was added to the suspension b4VO3Stirring ammonium metavanadate solid for 1 hour until the ammonium metavanadate solid is completely dissolved to form a suspension c; transferring the suspension c obtained in the fourth step to a normal-pressure microwave reactor with a reflux device again, controlling the reaction temperature at 100 ℃, adjusting the power of the equipment at 800 watts, and heating for 10min to obtain a suspension d subjected to secondary adsorption; in the secondary microwave reaction step, the core innovation point is that the vanadate is arranged at [ P6, 6, 6, 14]][Cl]The ionic liquid containing phosphine functional groups is further adsorbed on the surface of the graphene/multi-walled carbon nanotube under the action of microwave radiation, so that the ordered crystal growth along a specific crystal face is facilitated in the next reaction process; fifthly, adding a zinc nitrate solution with the volume of 50ml and the molar concentration of 0.20mol/L into the adsorbed suspension d, fully stirring for 20 minutes, continuously transferring the suspension into a normal-pressure microwave reactor with a reflux device, controlling the reaction temperature at 100 ℃, adjusting the heating power of equipment at 800 watts, heating for 8 hours, obtaining a black agglomerated suspension e, slowly cooling the obtained suspension e to the room temperature, washing the suspension e with distilled water for 4 times, rinsing the suspension e with ethanol for 1 time, and drying the suspension e in a vacuum drying oven at 80 ℃ for 24 hours; dried black solid sample: zinc vanadate nanorods/graphene/multiwalled carbon nanotubes; x-ray diffraction tests show that: the phase of the material is monoclinic phase m-ZnV2O6Corresponding to cell parameters of
Figure BSA0000216213380000131
Figure BSA0000216213380000132
And β 111.55 °, space point group: c2(No.5), the number of the ICDD-JCPDS card is No. 74-1262; SEM test shows that: m-ZnV2O6The nanorod is 40-80 nm in diameter and 20-30 microns in length, and is embedded on the surface of the graphene/multi-walled carbon nanotube in situ; HRTEM analysis and test show that m-ZnV2O6The growth direction of the nanorods is along [010 ]]Directionally dominant growth; sixthly, in order to test the energy storage performance of the zinc vanadate nanorod/graphene/multi-walled carbon nanotube in the zinc ion battery, the electrode material is assembled into a CR2032 button type batteryA pool; the working electrode is prepared by uniformly stirring a zinc vanadate nanorod/graphene/multi-walled carbon nanotube battery material, SP conductive carbon black and polyvinylidene fluoride powder according to a formula with the weight ratio of 8: 1, and the dispersing solvent is N-methyl pyrrolidone, and stirring for 2 hours to form a uniform paste; uniformly coating the aluminum foil on a high-purity aluminum foil, and drying the aluminum foil in a vacuum drying oven at 120 ℃ for 12 hours to obtain an electrode slice; the aqueous electrolyte is preferably 0.5mol/L ZnSO4A solution; the counter electrode is a metal zinc sheet with the purity of 99.99 percent; the test of 0.1C constant current charging and discharging performance and the test of cycling stability show that: the material has good zinc storage capacity and capacity retention rate, and the comprehensive performance obtains good and excellent effects.
Comparative example 2 of example 1 preparation of wuli juan. metal oxide/carbon composite fiber and electrochemical performance study [ D ]. hunan. Hunan pool university. 2012 a preparation method was provided with the experimental steps:
(a) dissolving ammonium metavanadate, metal salt and citric acid in deionized water according to a certain molar ratio, and heating, stirring and dissolving; then adding a solvent N, N-dimethylformamide with the same volume as the deionized water, adding polyvinylpyrrolidone (PVP), and magnetically stirring for 10-12h to obtain a spinning solution with a certain mass concentration;
(b) spinning the spinning solution by an electrostatic spinning device, wherein the rotating speed of a pump is 1mL & h < -1 >, the voltage is 26-30 KV, and the distance between a syringe needle and a receiving plate is 20cm, so as to obtain a precursor;
(c) drying the precursor in a drying oven at 80 ℃ for 12h, then calcining in a tube furnace, and carrying out heat treatment in a manner that: under inert atmosphere, heating at 2 deg.C for min-1, heating from room temperature to 600 deg.C, 700 deg.C and 800 deg.C respectively, keeping the temperature for 4h, and cooling to room temperature to obtain vanadate/carbon composite fiber.
The product prepared by the method has large size, the crystal structure is damaged after carbonization, and the quality of the obtained product is poor.
While example 1 is combined with comparative example 2 without motivation, and example 1 has clear innovativeness and is represented by: example 1: 0.1000g of graphene powder material, the reflux reaction temperature is 100 ℃, and the microwave power is 800 watts
First, to improve the materialThe conductive performance of the material is characterized in that a conductive carbon material is added in the experimental process; the carbon raw material is a high specific surface area graphene/multi-wall carbon nanotube material, and the specific surface area of the material is 1600m2The graphene ultrathin nanosheets are assembled by crosslinked graphene nanosheets with the interlayer spacing of 0.37nm, and single-walled carbon nanotubes with the diameter of 3-5 nm are inlaid on the surfaces of the graphene ultrathin nanosheets; secondly, weighing 0.1000g of graphene powder material at room temperature, and adding the graphene powder material into 50ml of distilled water; 0.2000g of trihexyltetradecylphosphine chloride ([ P6, 6, 6, 14) was additionally added][Cl]) Analyzing pure raw materials by using ionic liquid, and fully stirring for 1 hour to form uniform suspension a; thirdly, transferring the suspension a obtained in the second step into a 200ml quartz round-bottom flask, assembling the flask into a normal-pressure microwave reactor with a reflux device, controlling the reaction temperature at 100 ℃, adjusting the power of the device at 800 watts, and heating for 1 hour to obtain an adsorbed suspension b; in the step, the core innovation point is that under the action of a microwave field, the surface of the graphene/multi-walled carbon nanotube is effectively adsorbed with ionic liquid, so that experimental conditions are provided for the subsequent in-situ one-dimensional nano material oriented growth; fourthly, 0.5850g of NH was added to the post-adsorption suspension b4VO3Stirring ammonium metavanadate solid for 1 hour until the ammonium metavanadate solid is completely dissolved to form a suspension c; transferring the suspension c obtained in the fourth step to a normal-pressure microwave reactor with a reflux device again, controlling the reaction temperature at 100 ℃, adjusting the power of the equipment at 800 watts, and heating for 10min to obtain a suspension d subjected to secondary adsorption; in the secondary microwave reaction step, the core innovation point is that the vanadate is arranged at [ P6, 6, 6, 14]][Cl]The ionic liquid containing phosphine functional groups is further adsorbed on the surface of the graphene/multi-walled carbon nanotube under the action of microwave radiation, so that the ordered crystal growth along a specific crystal face is facilitated in the next reaction process; fifthly, adding a zinc nitrate solution with the solution volume of 50ml and the molar concentration of 0.20mol/L into the suspension d after adsorption, fully stirring for 20 minutes, continuously transferring the suspension into a normal-pressure microwave reactor with a reflux device, controlling the reaction temperature at 100 ℃, adjusting the heating power of the device at 800 watts, heating for 8 hours, obtaining a black agglomerated suspension e, slowly cooling the obtained suspension e to the room temperature, washing the suspension e with distilled water 4, and using ethanolRinsing for 1 time, and drying in a vacuum drying oven at 80 deg.C for 24 hr; dried black solid sample: zinc vanadate nanorods/graphene/multiwalled carbon nanotubes; x-ray diffraction tests show that: the phase of the material is monoclinic phase m-ZnV2O6Corresponding to cell parameters of
Figure BSA0000216213380000151
Figure BSA0000216213380000152
And β 111.55 °, space point group: c2(No.5), the number of the ICDD-JCPDS card is No. 74-1262; SEM test shows that: m-ZnV2O6The nanorod is 40-80 nm in diameter and 20-30 microns in length, and is embedded on the surface of the graphene/multi-walled carbon nanotube in situ; HRTEM analysis and test show that m-ZnV2O6The growth direction of the nanorods is along [010 ]]Directionally dominant growth; sixthly, in order to test the energy storage performance of the zinc vanadate nanorod/graphene/multi-walled carbon nanotube in the zinc ion battery, assembling the electrode material into a CR2032 button cell; the working electrode is prepared by uniformly stirring a zinc vanadate nanorod/graphene/multi-walled carbon nanotube battery material, SP conductive carbon black and polyvinylidene fluoride powder according to a formula with the weight ratio of 8: 1, and the dispersing solvent is N-methyl pyrrolidone, and stirring for 2 hours to form a uniform paste; uniformly coating the aluminum foil on a high-purity aluminum foil, and drying the aluminum foil in a vacuum drying oven at 120 ℃ for 12 hours to obtain an electrode slice; the aqueous electrolyte is preferably 0.5mol/L ZnSO4A solution; the counter electrode is a metal zinc sheet with the purity of 99.99 percent; the test of 0.1C constant current charging and discharging performance and the test of cycling stability show that: the material has good zinc storage capacity and capacity retention rate, and the comprehensive performance obtains good and excellent effects.

Claims (1)

1. The invention provides a ZnV (zinc-ion battery) grown by ionic liquid assisted in-situ compounding of specific crystal face2O6Method for preparing/GN-SWCNTS material from high specific surface area graphene/single-wall carbon nanotube material and trihexyltetradecylphosphine chloride [ P6, 6, 6, 14]][Cl]Taking ionic liquid, zinc nitrate and ammonium metavanadate as raw materials and extractingZnV growing on graphene surface in-situ composite specific crystal face by microwave radiation method2O6The material is taken as a zinc ion battery anode material to show good zinc storage performance, and a good technical effect is obtained; the method comprises the following steps:
firstly, in order to improve the conductivity of the material, a conductive carbon material is added in the experimental process; the carbon raw material is a graphene/multi-wall carbon nanotube material with high specific surface area, and the specific surface area of the material is 1200-1800 m2The graphene ultrathin nanosheets are assembled by crosslinked graphene nanosheets with the interlayer spacing of 0.37nm, and single-walled carbon nanotubes with the diameter of 3-5 nm are inlaid on the surfaces of the graphene ultrathin nanosheets;
secondly, weighing 0.1000-1.0000 g of graphene powder material at room temperature, and adding the graphene powder material into 50ml of distilled water; then adding 0.2000g of [ P6, 6, 6, 14] [ Cl ] ionic liquid analytically pure raw material, and fully stirring for 1 hour to form uniform suspension a;
thirdly, transferring the suspension a obtained in the second step into a 200ml quartz round-bottom flask, assembling the flask into a normal-pressure microwave reactor with a reflux device, controlling the reaction temperature to be 80-100 ℃, adjusting the power of the device to be 500-1200 watts, and heating for 1 hour to obtain an adsorbed suspension b; in the step, the core innovation point is that under the action of a microwave field, the surface of the graphene/multi-walled carbon nanotube is effectively adsorbed with ionic liquid, so that experimental conditions are provided for the subsequent in-situ one-dimensional nano material oriented growth;
fourthly, 0.5850g of NH was added to the post-adsorption suspension b4VO3Stirring ammonium metavanadate solid for 1 hour until the ammonium metavanadate solid is completely dissolved to form a suspension c; transferring the suspension c obtained in the fourth step into a normal-pressure microwave reactor with a reflux device again, controlling the reaction temperature to be 80-100 ℃, adjusting the power of the equipment to be 500-1200 watts, and heating for 10min to obtain a suspension d subjected to secondary adsorption; in the secondary microwave reaction step, the core innovation point is that the vanadate is arranged at [ P6, 6, 6, 14]][Cl]The ionic liquid containing phosphine functional groups is further adsorbed on the surface of the graphene/multi-walled carbon nanotube under the action of microwave radiation, so that the ordered crystal growth along a specific crystal face is facilitated in the next reaction process;
fifthly, adding a zinc nitrate solution with the volume of 50ml and the molar concentration of 0.20mol/L into the adsorbed suspension d, fully stirring for 20 minutes, continuously transferring the suspension into a normal-pressure microwave reactor with a reflux device, controlling the reaction temperature to be 80-100 ℃, adjusting the heating power of equipment to be 500-1200 watts, heating for 8 hours, obtaining a black agglomerated suspension e, slowly cooling the obtained suspension e to room temperature, washing the black agglomerated suspension e with distilled water for 4 times, rinsing the black agglomerated suspension e with ethanol for 1 time, and drying the black agglomerated suspension e in a vacuum drying oven at 80 ℃ for 24 hours; dried black solid sample: zinc vanadate nanorods/graphene/multiwalled carbon nanotubes; x-ray diffraction tests show that: the phase of the material is monoclinic phase m-ZnV2O6Corresponding to cell parameters of
Figure FSA0000216213370000021
And β 111.55 °, space point group: c2(No.5), the number of the ICDD-JCPDS card is No. 74-1262; SEM test shows that: m-ZnV2O6The nanorod is 40-80 nm in diameter and 20-30 microns in length, and is embedded on the surface of the graphene/multi-walled carbon nanotube in situ; HRTEM analysis and test show that m-ZnV2O6The growth direction of the nanorods is along [010 ]]Directionally dominant growth;
sixthly, in order to test the energy storage performance of the zinc vanadate nanorod/graphene/multi-walled carbon nanotube in the zinc ion battery, assembling the electrode material into a CR2032 button cell; the working electrode is prepared by uniformly stirring a zinc vanadate nanorod/graphene/multi-walled carbon nanotube battery material, SP conductive carbon black and polyvinylidene fluoride powder according to a formula with the weight ratio of 8: 1, and the dispersing solvent is N-methyl pyrrolidone, and stirring for 2 hours to form a uniform paste; uniformly coating the aluminum foil on a high-purity aluminum foil, and drying the aluminum foil in a vacuum drying oven at 120 ℃ for 12 hours to obtain an electrode slice; the aqueous electrolyte is preferably 0.5mol/L ZnSO4A solution; the counter electrode is a metal zinc sheet with the purity of 99.99 percent; the test of 0.1C constant current charging and discharging performance and the test of cycling stability show that: the material has good zinc storage capacity and capacity retention rate, and the comprehensive performance obtains good and excellent effects.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112875756A (en) * 2021-02-19 2021-06-01 苏州科技大学 Manganese molybdate nanoflower/graphene three-dimensional structure and high-specific-volume supercapacitor performance improvement method
CN114300675A (en) * 2021-12-31 2022-04-08 欣旺达电动汽车电池有限公司 Positive electrode material, preparation method thereof and water-based zinc ion battery

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103130277A (en) * 2013-02-28 2013-06-05 安徽工业大学 Method for preparing zinc vanadate nanorod
CN103553141A (en) * 2013-11-06 2014-02-05 太原理工大学 Method for synthesizing ferrous acid manganese nanowire material through ionic liquid assisted microwave radiation method
CN105655670A (en) * 2015-12-30 2016-06-08 华北理工大学 Controllable preparation method of manganese oxide super long nanowire/graphene electrocatalyst for magnesium air battery
CN105655602A (en) * 2015-12-30 2016-06-08 华北理工大学 Design synthesis method of nanocubic electrocatalyst with Mn2O3 and Mn3O4 mixture phase and for magnesium air battery
US20180212241A1 (en) * 2017-01-23 2018-07-26 Chung Yuan Christian University Sodium secondary battery

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103130277A (en) * 2013-02-28 2013-06-05 安徽工业大学 Method for preparing zinc vanadate nanorod
CN103553141A (en) * 2013-11-06 2014-02-05 太原理工大学 Method for synthesizing ferrous acid manganese nanowire material through ionic liquid assisted microwave radiation method
CN105655670A (en) * 2015-12-30 2016-06-08 华北理工大学 Controllable preparation method of manganese oxide super long nanowire/graphene electrocatalyst for magnesium air battery
CN105655602A (en) * 2015-12-30 2016-06-08 华北理工大学 Design synthesis method of nanocubic electrocatalyst with Mn2O3 and Mn3O4 mixture phase and for magnesium air battery
US20180212241A1 (en) * 2017-01-23 2018-07-26 Chung Yuan Christian University Sodium secondary battery

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
YAN SUN等: ""Electrochemically active, novel layered m-ZnV2O6 nanobelts for highly rechargeable Na-ion energy storage"", 《ELECTROCHIMICA ACTA》 *
YAN SUN等: ""Ultralong monoclinic ZnV2O6 nanowires: their shape-controlled synthesis，new growth mechanism, and highly reversible lithium storage in lithium-ion batteries"", 《RSC ADVANCES》 *
顾媛媛等: ""钒酸锌纳米材料光催化性能研究"", 《长春工业大学学报》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112875756A (en) * 2021-02-19 2021-06-01 苏州科技大学 Manganese molybdate nanoflower/graphene three-dimensional structure and high-specific-volume supercapacitor performance improvement method
CN112875756B (en) * 2021-02-19 2022-09-06 苏州科技大学 Manganese molybdate nanoflower/graphene three-dimensional structure and high-specific-volume supercapacitor performance improvement method
CN114300675A (en) * 2021-12-31 2022-04-08 欣旺达电动汽车电池有限公司 Positive electrode material, preparation method thereof and water-based zinc ion battery
CN114300675B (en) * 2021-12-31 2023-08-15 欣旺达电动汽车电池有限公司 Positive electrode material, preparation method thereof and water-based zinc ion battery

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